US10787591B2 - Composites including silicon-oxy-carbide layers and methods of making the same - Google Patents

Composites including silicon-oxy-carbide layers and methods of making the same Download PDF

Info

Publication number
US10787591B2
US10787591B2 US13/833,686 US201313833686A US10787591B2 US 10787591 B2 US10787591 B2 US 10787591B2 US 201313833686 A US201313833686 A US 201313833686A US 10787591 B2 US10787591 B2 US 10787591B2
Authority
US
United States
Prior art keywords
composite
soc
layer
substrate
soc layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US13/833,686
Other languages
English (en)
Other versions
US20130288044A1 (en
Inventor
Thomas K. Tsotsis
Marvi A. Matos
Alpana Ranade
Laura M. Murphy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Boeing Co
Original Assignee
Boeing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Boeing Co filed Critical Boeing Co
Assigned to THE BOEING COMPANY reassignment THE BOEING COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MATOS, Marvi A., RANADE, ALPANA, MURPHY, LAURA M., TSOTSIS, THOMAS K.
Priority to US13/833,686 priority Critical patent/US10787591B2/en
Priority to EP13783121.0A priority patent/EP2844783B1/en
Priority to JP2015510287A priority patent/JP6421114B2/ja
Priority to PCT/US2013/034435 priority patent/WO2014007894A2/en
Priority to EP18188957.7A priority patent/EP3428311B1/en
Priority to AU2013287214A priority patent/AU2013287214B2/en
Publication of US20130288044A1 publication Critical patent/US20130288044A1/en
Priority to JP2018159930A priority patent/JP2019022984A/ja
Publication of US10787591B2 publication Critical patent/US10787591B2/en
Application granted granted Critical
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/453—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

Definitions

  • the presently disclosed subject matter relates to high-temperature polymer composites including at least one silicon-oxy-carbide film deposited by atmospheric plasma deposition.
  • high-temperature polymeric materials can be limited at elevated temperatures (e.g., greater than about 350° F.) in applications that require long exposures (e.g., greater than 1000 hours) because the polymeric materials may react with oxygen under these conditions. This interaction of the polymeric materials with oxygen can result in undesirable degradation and diminishing material properties that can be difficult to predict.
  • FIG. 2 shows a depiction of such increased surface degredation.
  • thermo-oxidative stability Intuitively it would seem that protecting a material's surface from oxygen diffusion would improve its thermo-oxidative stability and, indeed, some studies verify this supposition.
  • aluminum foil was used to coat Celion 6000/PMR-15 composites and did find that a thin coating did provide significant protection from oxidation.
  • the use of an expanded graphite barrier reduced the rate of oxidative degradation of PMR-15 resin such that the thermo-oxidative stability increased by up to 25%.
  • high-temperature barrier coatings e.g., oxygen-barrier
  • adhesion-promoting coatings e.g., interlayers
  • thermo-oxidative coating comprises a silicon-oxy-carbide (SOC) layer generally having a thickness from about 50 nm to about 12 microns and covering at least one surface of the polymeric substrate.
  • SOC silicon-oxy-carbide
  • the SOC layer is formed by atmospheric plasma deposition.
  • barrier layers e.g., oxygen-barrier layers
  • Certain aspects provide composites that beneficially demonstrate an increased level of thermo-oxidative stability relative of composites of the same polymeric substrate being devoid of a thermo-oxidative barrier coating according to aspects of the present disclosure.
  • the present disclosure provides composites including an adhesion-promoting layer comprising a silicon-oxy-carbide (SOC) layer having a thickness generally from about 50 nm to about 12 microns deposited onto at least one surface of a polymeric matrix substrate.
  • SOC silicon-oxy-carbide
  • the SOC layer is formed by atmospheric plasma deposition.
  • the adhesion-promoting layer can be used to bind a known (or prospective) oxygen-barrier layer (OBL) onto the composite. That is, the OBL can be deposited in a manner substantially (or fully) overlying the adhesion-promoting layer such that the adhesion-promoting layer is sandwiched between the polymeric matrix substrate and the OBL.
  • OBL oxygen-barrier layer
  • the adhesion-promoting layer functions at least in one respect as a tailorable tie-layer for the polymeric matrix substrate and the OBL.
  • the adhesion-promoting layer increases the degree to which the OBL is attached to the composite.
  • the adhesion-promoting layer according to aspects of the present disclosure can increase the bond strength of the OBL to the polymeric substrate relative to the bond strength of the same OBL directly deposited onto the same polymeric substrate.
  • thermo-oxidative barrier coating comprising a SOC layer, preferably having a thickness from about 50 nm to about 12 microns, onto at least one surface of a polymeric matrix substrate via atmospheric plasma deposition.
  • the thermo-oxidative barrier coating beneficially reduces the level and/or rate of oxygen diffusion into the polymeric matrix resin. Consequently, certain aspects of the present disclosure demonstrate an increased level of thermo-oxidative stability relative of composites of the same polymeric substrate being devoid of a thermo-oxidative barrier coating according to aspects of the present disclosure.
  • composites are produced by depositing an adhesion-promoting layer comprising a SOC, preferably having a thickness from about 50 nm to about 12 microns, onto at least one surface of a polymeric matrix substrate followed by depositing an OBL substantially overlying the adhesion-promoting layer.
  • the adhesion-promoting layer in at least one respect, functions as a tie-layer to facilitate a stronger and longer-lasting bond of the OBL to the polymeric matrix substrate.
  • the adhesion-promoting layer can be specifically tailored to tie dissimilar materials (e.g., the OBL layer being dissimilar to the polymeric matrix substrate as realized by a relatively weak or non-existent direct bond between the two components).
  • the SOC layer is formed by atmospheric plasma deposition, which enables a high level of tailoring for specific polymeric matrix substrates, OBL, and/or specific applications for the resulting composite.
  • FIG. 1 shows a schematic of oxygen diffusion into a composite and resulting near-surface degradation after long-term, thermo-oxidative exposure
  • FIG. 2 shows a schematic of surface degradation due to thermo-oxidative aging.
  • FIG. 3 illustrates a composite aspect comprising a thermo-oxidative barrier coating comprising a silicon-oxy-carbide (SOC) layer deposited onto a polymeric matrix substrate;
  • SOC silicon-oxy-carbide
  • FIG. 4 illustrates a composite aspect comprising an adhesion-promoting layer comprising a silicon-oxy-carbide (SOC) layer sandwiched between at least one surface of a polymeric matrix substrate and an oxygen-barrier layer;
  • SOC silicon-oxy-carbide
  • FIG. 5 illustrates a general flow diagram for a method of forming a composite aspect in which an SOC layer is provided as an oxygen-barrier layer (OBL);
  • OLB oxygen-barrier layer
  • FIG. 6 illustrates a general flow diagram for a method of forming a composite aspect in which an SOC layer is provided as an adhesion-promoting layer;
  • FIG. 7A provides a general schematic of atmospheric plasma deposition that can be employed in forming SOC coating aspects
  • FIG. 7B provides a general schematic of an atmospheric plasma deposition device including a showerhead-type discharge head aspect
  • FIGS. 8A-8I are Fourier transform infrared spectroscopy (FTIR) spectra for SOC layers (i) prior to aging, (ii) after about 3432 hours of aging, and (iii) after about 7752 hours of aging.
  • FTIR Fourier transform infrared spectroscopy
  • Silicon-oxy-carbides include Si—O—C as their main skeleton.
  • Aspects of the present disclosure comprise high-temperature polymer composites including at least one SOC coating or layer deposited onto a polymeric matrix substrate by atmospheric plasma deposition as well as systems and methods of applying SOC layers on polymeric matrix substrates to form composites demonstrating an improved level of thermo-oxidative stability.
  • atmospheric plasma deposition beneficially enables the tailoring of the resulting SOC layers so that they can function either (or both) (i) as a thermo-oxidative barrier coating preventing or significantly mitigating the level of oxygen that diffuses into the polymeric matrix substrate or (ii) an adhesion-promoting layer increasing the degree of adherence or bonding of an oxygen-barrier layer (OBL) to the polymeric matrix substrate.
  • Additional benefits of using atmospheric plasma deposition include the ability to provide uniform coatings, particularly on complex and/or contoured surfaces, and a lower cost of capital equipment than traditional thin film vacuum deposition methods.
  • a composite can include a SOC layer sandwiched between the polymeric matrix substrate and a commercially known or viable OBL in which the SOC layer functions both as a “tie-layer” to attach two dissimilar components (e.g., substrate and OBL) and also as a secondary oxygen-barrier to prevent oxygen diffusion into the polymeric matrix substrate.
  • the SOC layers are preferably capable of withstanding high-temperature (e.g., 350-700° F.) exposures that are either non-porous, strain-resistant, or a combination thereof.
  • the SOC layers can beneficially enhance a composite's thermo-oxidative stability.
  • Composites including one or more SOC layers according to certain aspects of the present disclosure exhibit a substantially reduced level of oxygen diffusion into the polymeric matrix substrate. That is, the one or more SOC layers significantly retard thermo-oxidative degradation. In this regard, the one or more SOC layers prevents or substantially reduces the level of oxygen diffusing into the polymeric matrix substrate.
  • the SOC layers can be deposited onto the polymeric matrix substrate utilizing atmospheric plasma deposition.
  • Utilization of atmospheric plasma deposition enables the creation of tailorable, thermo-oxidative stable, strain-resistant coatings to improve the in-service durability and useful service temperature of high-temperature polymeric composites.
  • the use of atmospheric plasma deposition enables the formation of a dense and durable thin film or coating directly onto substrates and to complex (e.g., contoured) shapes as compared to other approaches.
  • certain aspects of the present disclosure enable the use of high-performance materials to produce durable, non-permeable, strain-resistant oxygen-barriers or adhesion-promoting layers.
  • aspects of the present disclosure provide for the formation of tailored coatings below the micron scale to obtain desired features.
  • a further advantage of aspects of the present disclosure lies in the ability to directly apply an SOC coating to complex shapes to form composite of such complex shapes.
  • atmospheric plasma deposition can be provided as a mobile system so that coatings can be applied on site rather than in a lab or factory, if so desired.
  • SOC coatings according to aspects of the present disclosure can comprise a thickness of at least any of the following: 10, 50, 100, 200, 300, 400, and 500 nm; and at most about any of the following: 12000, 10000, 50000, 1000, 900, 800, 700, 600, 500, and 400 nm (e.g., 10-12000 nm, 10-10000 nm, 50-800 nm, 50-500 nm, 10-200 nm, etc.).
  • SOC coatings according to certain aspects of the present disclosure can comprise a thickness from about 50 nm to about 12 microns.
  • the respective carbon, silicon, and oxygen content of SOC coatings can be varied in view of a particularly intended application.
  • the SOC layers can include a carbon content comprising at least any of the following: 3, 5, 10, 20, 30, 40, 50, and 60%; and at most about any of the following: 70, 60, 50, 40, 30, 25%, 20%, ands 10% (e.g., 5-70%, 20-70%, 10-40%, 50-70%, 3-50%, 3-25%, 3-10%, etc.).
  • the SOC coatings can include a silicon content comprising at least any of the following: 3, 5, 10, 20, 30, 40, 50, and 60%; and at most about any of the following: 70, 60, 50, 40, 30, 25%, 20%, ands 10% (e.g., 5-70%, 20-70%, 10-40%, 50-70%, 3-50%, 3-25%, 3-10%, etc.).
  • the SOC coatings can include an oxygen content comprising at least any of the following: 3, 5, 10, 20, 30, 40, 50, and 60%; and at most about any of the following: 70, 60, 50, 40, 30, 25%, 20%, ands 10% (e.g., 5-70%, 20-70%, 10-40%, 50-70%, 3-50%, 3-25%, 3-10%, etc.).
  • the SOC coating or layers according to aspects of the present disclosure are created via atmospheric plasma deposition.
  • a variety of chemical precursors can be used in atmospheric plasma deposition for creating SOC layers according to aspects of the present disclosure.
  • siloxanes and organosilanes can be employed in certain aspects.
  • a few exemplary chemical precursors can include octamethylcyclotetrasiloxane (OMCTS), tetramethylcyclotetrasiloxane (TMCTS), hexamethyldisiloxane (HMDSO), 1,2-bis(triethoxysilyl)ethane (BTESE), tetraethyl orthosilicate (TEOS), hexamethyldisilizane (HMDSN), tetrarnethyldisiloxane (TMDSO), or combinations thereof.
  • the polymeric matrix substrate can comprise a polyimide, a bismaleimide, a benzoxazine, a thermoplastic (e.g., a polyetheretherketone, polyetherketoneketone, etc.), an epoxy, a cyanate ester, or combinations thereof.
  • the polymeric matrix substrate comprises a polyimide, preferably a polyimide recognized as being suitable for high-performance and/or high-temperature applications.
  • polyimides suitable for composite fabrication according to certain aspects of the present disclosure include those disclosed in U.S. Pat. No. 3,745,149 (Serafini et al.), U.S. Pat. No. 5,338,827 (Serafini et al.), U.S. Pat. No. 5,171,822 (Pater), U.S. Pat. No. 5,081,198 (Pater et al.), U.S. Pat. No. 7,041,778 (Curliss et al.), U.S. Pat. No.
  • Embodiments of the disclosure are directed to fiber reinforced polymer matrixes.
  • U.S. Pat. No. 3,745,149 describes a composite comprising graphite fibers impregnated with a polyimide resin.
  • U.S. Pat. No. 5,338,827 describes polyimide resins reinforced with fibers, such as carbon fibers including graphite, ceramics, including glass, quartz, alumina, silica, and silicon carbide.
  • U.S. Pat. No. 5,171,822 describes graphite fiber reinforced PMR polyimide composites.
  • U.S. Pat. No. 5,081,198 describes graphite fiber reinforced polyimide composites in which multiple plies of prepreg are stacked unidirectionally and then cured.
  • U.S. Pat. No. 5,654,396 describes prepregs, and composites prepared therefrom, in which polyimide oligomers are reinforced with woven fabrics having fibers that may be continuous or discontinuous, and may be ceramic, organic, carbon (graphite),
  • the present disclosure provides composites comprising a polymeric matrix substrate and a thermo-oxidative barrier coating.
  • the thermo-oxidative coating comprises a SOC layer created by atmospheric plasma deposition.
  • the SOC layer has a thickness from about 100 to about 900 nm and covers at least one surface of the polymeric substrate.
  • the SOC layer beneficially can reduce (or virtually eliminate) the amount of oxygen that diffuses into the polymeric matrix substrate.
  • thermo-oxidative stability test can include placing samples (e.g., SOC-coated polymeric matrix substrates) in a chamber through which a constant flow of air travels at a rate sufficient to refresh the chamber volume at a rate of 5 times/hour.
  • the test temperature, pressure, and time can be selected to result in a measurable degradation of an unprotected (uncoated) polymeric matrix substrate for direct comparison.
  • the oxygen-barrier capability of the SOC coating can be determined by the weight loss of protected composite samples relative to unprotected composite samples.
  • Thermo-oxidative Stability is the ability of the composite to withstand elevated temperatures in an oxygen-containing environment, such as air, with minimal loss of weight and/or properties. Since, in a composite, compression strength is a resin-dominated property, the retention of compression strength after long-time exposures to high temperatures is monitored as a measure of TOS. Weight loss over time can also be used as a measure. Polymers can degrade through mechanisms, such as volatilization, resulting in a composite having reduced mass due to this loss of polymer.
  • One test used herein to measure TOS includes placing a plaque of polymeric or composite material in a chamber, increasing the temperature and pressure within the chamber to a predetermined temperature and pressure, and holding these conditions for up to several thousand hours with multiple atmospheric changes over the course of the test.
  • the plaques are then removed and tested for weight loss and retention of compression and/or shear strength.
  • the weight loss and retention of compression strength reflect service conditions in high-performance environments and provide a measure of the longer-term stability of the polymeric material.
  • a higher TOS is important for material that will be used at a high temperature in air for long periods of time.
  • Composites in accordance with certain aspects of the present disclosure, can comprise a TOS comprising less than at least any of the following: 10%, 7%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, and 0% weight loss (e.g., 0.1-10%, 0.1-7%, etc.) relative to a composite comprising the same polymeric substrate and being devoid of a thermo-oxidative barrier layer comprising an SOC layer in accordance with aspects of the present disclosure.
  • a TOS comprising less than at least any of the following: 10%, 7%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, and 0% weight loss (e.g., 0.1-10%, 0.1-7%, etc.) relative to a composite comprising the same polymeric substrate and being devoid of a thermo-oxidative barrier layer comprising an SOC layer in accordance with aspects of the present disclosure.
  • FIG. 3 illustrates a composite according to one aspect of the present disclosure comprising a thermo-oxidative barrier coating 15 comprising a SOC layer deposited onto a polymeric matrix substrate 10 .
  • the present disclosure provides composites including an adhesion-promoting layer comprising a SOC layer deposited via atmospheric plasma deposition onto at least one surface of a polymeric matrix substrate.
  • the adhesion-promoting layer can be used to bind a known (or prospective) oxygen-barrier layer (OBL) onto the composite. That is, the OBL can be deposited in a manner substantially (or fully) overlying the adhesion-promoting layer such that the adhesion-promoting layer is sandwiched between the polymeric matrix substrate and the OBL.
  • OBL oxygen-barrier layer
  • the adhesion-promoting layer functions at least in one respect as a tailorable tie-layer for the polymeric matrix substrate and the OBL.
  • the adhesion-promoting layer increases the degree to which the OBL is attached to the composite.
  • the adhesion-promoting layer according to aspects of the present disclosure can increase the bond strength of the OBL to the polymeric substrate relative to the bond strength of the same OBL directly deposited onto the same polymeric substrate.
  • the OBL can include currently known (or OBL materials developed in the future) OBL materials that reduce (or virtually eliminates) oxygen diffusion into the polymeric matrix substrate.
  • OBL materials can comprise metallic materials, ceramic materials, or combinations thereof.
  • Exemplary materials that may be used to form the OBL layer can include known oxygen-barriers such as silicon oxides, aluminum, and aluminum oxides.
  • the adhesion-promoting layer increases the bond strength of the OBL to the polymeric substrate relative to the bond strength of the same OBL directly deposited onto the same polymeric substrate.
  • composites can comprise a first bond strength between the polymeric substrate and the SOC layer and a second bond strength between the SOC layer and the OBL.
  • the first and second bond strengths each being greater than that of a comparative bond strength directly between the same OBL and the same polymeric substrate.
  • the incorporation of the adhesion-promoting layer helps ensure that an OBL material stays attached to the polymeric matrix substrate to improve the thermo-oxidative stability of the composite.
  • a composite can include a SOC layer sandwiched between the polymeric matrix substrate and a commercially known or viable OBL in which the SOC layer functions both as a “tie-layer” to attach two dissimilar components (e.g., substrate and OBL) and also as a secondary oxygen-barrier to prevent oxygen diffusion into the polymeric matrix substrate.
  • FIG. 4 illustrates a composite according to one aspect of the present disclosure comprising an adhesion-promoting layer 20 comprising a SOC layer deposited onto at least one surface of a polymeric matrix substrate 10 .
  • the adhesion-promoting layer 20 is sandwiched between at least one surface of a polymeric matrix substrate 10 and an OBL 30 .
  • the present disclosure provides methods of fabricating composites according to aspects of the present disclosure.
  • methods of forming composites include a step of depositing a thermo-oxidative barrier coating comprising a SOC layer directly onto at least one surface of a polymeric matrix substrate via atmospheric plasma deposition.
  • the thermo-oxidative barrier coating beneficially reduces the level and/or rate of oxygen diffusion into the polymeric matrix resin. Consequently, certain aspects of the present disclosure demonstrate an increased level of thermo-oxidative stability relative of composites of the same polymeric substrate being devoid of a thermo-oxidative barrier coating according to aspects of the present disclosure.
  • certain aspects of the present disclosure can include a step of providing one or more polymeric substrates 100 followed by depositing a thermo-oxidative barrier coating comprising a SOC layer 150 directly onto at least one surface of the polymeric substrate to provide a composite.
  • the polymeric substrates can be pre-cleaned by traditional physical or chemical methods and/or plasma pretreated prior to depositing an SOC layer onto the polymeric substrate.
  • the SOC layer can provide adequate thermo-oxidative stability to the resulting composite that a traditionally employed thermo-oxidative barrier layer can be avoided if desired.
  • composites are produced by depositing an adhesion-promoting layer comprising a SOC onto at least one surface of a polymeric matrix substrate followed by depositing an OBL substantially overlying the adhesion-promoting layer.
  • the adhesion-promoting layer in at least one respect, functions as a tie-layer to facilitate a stronger and longer-lasting bond of the OBL to the polymeric matrix substrate.
  • the adhesion-promoting layer can be specifically tailored to tie dissimilar materials (e.g., the OBL layer being dissimilar to the polymeric matrix substrate as realized by a relatively weak or non-existent direct bond between the two components).
  • the SOC layer is formed by atmospheric plasma deposition, which enables a high level of tailoring for specific polymeric matrix substrates, OBL, and/or specific applications for the resulting composite.
  • the OBL reduces oxygen diffusion into the polymeric substrate and can comprise known OBL materials such as various metallic materials, ceramic materials, or combinations thereof.
  • the OBL can be deposited on top (e.g., overlying) the adhesion-promoting layer by any technique known for depositing such materials.
  • the adhesion-promoting layer beneficially increases the bond strength of the OBL to the polymeric matrix substrate relative to the bond strength of the same OBL when directly deposited onto the same polymeric substrate.
  • the SOC layer functions as an interlayer over which a different layer (e.g., a traditional OBL) can be deposited.
  • certain aspects of the present disclosure in which the SOC layer is sandwiched between the polymeric substrate and a traditional OBL can include a step of providing one or more polymeric substrates 200 followed by depositing an adhesion-promoting layer comprising a SOC 250 onto at least one surface of the polymeric substrate.
  • the SOC coated polymeric substrate can then be subjected to an OBL deposition step 275 in which a traditional OBL is deposited over the top of the SOC layer such that the SOC layer is sandwiched between the OBL and the polymeric substrate to provide a composite according to certain aspects of the present disclosure.
  • the polymeric substrates can be pre-cleaned by traditional physical or chemical methods and/or plasma pretreated prior to depositing an SOC layer onto the polymeric substrate.
  • the SOC coatings/layers are created by atmospheric plasma deposition.
  • One of the benefits of using atmospheric plasma deposition is that the relatively large production of chemically reactive species, such as atomic oxygen, enables the precursor to be mixed downstream in the plasma afterglow where it can react with the reactive neutrals from the plasma to produce a coating on the substrate.
  • Atmospheric plasma deposition beneficially generates much greater reactive species concentrations than more traditional deposition techniques and can be used in a remote or downstream mode.
  • One suitable atmospheric plasma deposition system suitable for deposited an SOC coating onto a polymeric matrix substrate is ATOMFLOTM Model 400 with Precursor Delivery System from Surfx® Technologies LLC (USA).
  • Chemical precursor materials for creation of SOC layers in accordance with aspects of the present disclosure can generally comprise silanes, organosilanes, or combination thereof.
  • a few exemplary chemical precursors suitable for certain aspects include octamethylcyclotetrasiloxane (OMCTS), tetramethylcyclotetrasiloxane (TMCTS), hexamethyldisiloxane (HMDSO), 1,2-bis(triethoxysilyl)ethane (BTESE), tetraethyl orthosilicate (TEOS), hexamethyl di silazane (HMDSN), tetramethyldi si oxane (TMDSO), or combinations thereof.
  • OCTS octamethylcyclotetrasiloxane
  • TCTS tetramethylcyclotetrasiloxane
  • HMDSO hexamethyldisiloxane
  • BTESE 1,2-bis(triethoxysilyl)ethane
  • atmospheric plasma deposition has several parameters that can be adjusted in unison or independently of each other to tailor the resulting SOC coating for a desired application.
  • the following operating parameters and associated ranges for each are merely exemplary of the operating conditions that can be employed to create SOC layers according to aspects of the present disclosure.
  • the height of the plasma applicator head from the substrate being coated can be adjusted as desired, for example, from about 1 mm to 1 cm (e.g., 2-7 mm, 3-6 mm).
  • the helium or argon (as the primary gas) flow rate can be varied from about 20 to 50 liters per minute (LPM) (e.g., 20-40, 25-35 LPM).
  • LPM liters per minute
  • the plasma power can be varied from about 80 W to 180 W (e.g, 100-150 W, 120-150 W).
  • Oxygen gas flow can range, for example, from 0.1 to 1 LPM.
  • the bubbler flow rate of the inert gas e.g., helium
  • the dilution flow rate of inert gas can range from about 0.5 to 5.0 LPM.
  • the temperature of the chemical precursor can vary from room temperature up to the boiling point of the particular chemical being utilized as the chemical precursor.
  • the plasma applicator head is typically attached to a robotic arm that has been programmed to apply the SOC coating onto a given space of the substrate.
  • the speed at which the robotic arm moves can be varied as well. For instance, the speed at which the robotic arm moves can range from 10-100 mm/s.
  • FIG. 7A provides a general schematic of an atmospheric deposition device in accordance with certain aspects of the present disclosure.
  • the atmospheric-plasma deposition device 50 includes an outer electrode 52 which is electrically grounded and an inner electrode 54 to which an external voltage is applied.
  • the external voltage can be supplied by a high-frequency, high-voltage generator 57 .
  • the generator 57 can supply the inner electrode 54 with a voltage in the order of, for example, 5 to 30 kV and the frequency of the voltage can range, for example, from 10 to 20 kHz.
  • the atmospheric plasma deposition device 50 includes a plasma gas/working gas inlet stream 56 entering a first end of the device 50 .
  • the plasma gas/working gas inlet stream 56 comprises helium gas, oxygen gas, or a mixture thereof.
  • a plasma discharge 58 is generally located at an end of the device 50 opposite to the plasma gas/working gas inlet stream 56 .
  • a plasma stream 60 exits the plasma discharge 58 of the device 50 .
  • One or more chemical precursors 62 can be introduced into the plasma steam 60 via precursor inlets 64 .
  • an SOC layer 15 can be deposited onto the surface of a polymeric substrate 10 .
  • FIG. 7A illustrates a device 50 providing a single discharge steam (e.g., plasma discharge 58 in FIG. 7A )
  • certain preferred aspects utilize a device comprising a showerhead-type configuration in which multiple plasma discharges are provided.
  • FIG. 7B illustrates a device comprising a showerhead-type configuration in which multiple plasma discharges are provided.
  • an atmospheric-plasma deposition device 50 can comprise a showerhead-type discharge head 152 including multiple discharge orifices 158 .
  • the power supply 157 and the chemical precursors 162 can be connected to the top of the device 50 .
  • the chemical precursors can be delivered inside the head to the plasma and the afterglow region 160 is where the chemical reactions and film deposition occur.
  • One commercially available device including a showerhead-type configuration in which multiple plasma discharges are provided includes ATOMFLOTM Model 400 from Surfx® Technologies LLC (USA).
  • a total of eight panels had a SOC layer, ranging from about 200-500 nm thick, deposited thereon by atmospheric plasma deposition utilizing ATOMFLOTM Model 400 with Precursor Delivery System from Surfx® Technologies LLC (USA) to form the SOC layers in each of these examples.
  • the chemical precursors utilized were TMCTS and OMCTS.
  • a pretreatment step was conducted prior to deposition of the SOC layer onto the polyimide substrate.
  • the polyimide substrate was pretreated at a 50% power rating for 4 minutes March Plasmod GCM-200 with air as the plasma gas.
  • a ninth panel ( FIG. 8I ) was prepared and tested to provide a comparison to the eight panels having a SOC deposited thereon by atmospheric plasma deposition.
  • the ninth panel was provided coated with a vacuum CVD film.
  • Table 1 The operating variables that were modified from run to run, as well as respective values, are summarized in Table 1 below.
  • Table 2 provides a summary of the operating parameters of atmospheric plasma deposition that were held as fixed conditions during all runs. It should be noted, however, that the operating parameters that were selected to be fixed conditions among the eight run need not necessarily be fixed or set at these particular values.
  • the height between the plasma-deposition source and the closest surface of the polyimide substrate can readily be varied from the 5-mm height employed in the exemplary runs discussed herein.
  • the height of the deposition source above the substrate can be varied from 1 mm to 1 cm.
  • Table 3 provides a quick summary of the times used to coat a SOC layer onto a 100 mm ⁇ 138.5 mm polyimide substrate. It should be noted, however, that the deposition rates and/or density of the resulting SOC layer can be tailored by adjusting one or more of the operating parameters of the atmospheric plasma deposition.
  • each of the samples was subjected to testing for oxygen-barrier functionality at 450° F. for about 7,752 hours with weight loss data obtained after about 3,432 hours of exposure. These tests were conducted to illustrate the ability of the respective SOC coatings to stay attached to the polyimide substrate and the ability to prevent weight loss due to oxidation.
  • the SOC layers were deposited using OMCTS and TMCTS precursors with atmospheric plasma and the “CVD” sample was deposited with OMCTS in a vacuum chamber. The results of this additional testing are summarized in Table 4.
  • Additional testing comprising Fourier transform infrared spectroscopy (FTIR) was conducted on the SOC layers at the following three points of time: (1) prior to being subjected to aging process as discussed above; (2) after about 3,432 hours of being subjected to aging; and (3) after about 7,752 hours of being subjected to aging.
  • the respective FTIR spectra for each sample are provided in FIGS. 8A-8I .
  • Particularly preferred aspects according to certain aspects exhibit stability in the FTIR spectra over the time of aging/exposure. For a given panel, that is, a comparison of the FTIR spectrum representative of the unaged (e.g., no aging) panel and subsequent FTIR spectra representative of aged panel should not change significantly.
  • the SOC coatings can be considered stable when only minor (or preferably no) changes in the FTIR spectra from unaged to aged are compared. In such instances, the SOC layers can be considered stable and not oxidizing or thermally degrading during the test period. To the contrary, FTIR spectra that show large differences from the unaged to the aged are not particularly desirable as they are chemically changing as they age. Stated differently, changes in FTIR spectra after different amounts of aging indicate that the chemical composition of the surface is changing due to reaction with oxygen and other molecules. The FTIR spectra for the aspects associated with FIGS. 8C, 8D, and 8G show the least change in chemical composition after exposure to elevated temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)
  • Ceramic Products (AREA)
  • Physical Vapour Deposition (AREA)
  • Carbon And Carbon Compounds (AREA)
US13/833,686 2012-04-30 2013-03-15 Composites including silicon-oxy-carbide layers and methods of making the same Active 2035-12-18 US10787591B2 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US13/833,686 US10787591B2 (en) 2012-04-30 2013-03-15 Composites including silicon-oxy-carbide layers and methods of making the same
EP18188957.7A EP3428311B1 (en) 2012-04-30 2013-03-28 Composites including silicon-oxy-carbide layers and methods of making the same
JP2015510287A JP6421114B2 (ja) 2012-04-30 2013-03-28 シリコンオキシカーバイド層を含む複合材料、及び複合材料を形成する方法
PCT/US2013/034435 WO2014007894A2 (en) 2012-04-30 2013-03-28 Composites including silicon-oxy-carbide layers and methods of making the same
EP13783121.0A EP2844783B1 (en) 2012-04-30 2013-03-28 Composites including silicon-oxy-carbide layers and methods of making the same
AU2013287214A AU2013287214B2 (en) 2012-04-30 2013-03-28 Composites including silicon-oxy-carbide layers and methods of making the same
JP2018159930A JP2019022984A (ja) 2012-04-30 2018-08-29 シリコンオキシカーバイド層を含む複合材料、及び複合材料を形成する方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261640293P 2012-04-30 2012-04-30
US13/833,686 US10787591B2 (en) 2012-04-30 2013-03-15 Composites including silicon-oxy-carbide layers and methods of making the same

Publications (2)

Publication Number Publication Date
US20130288044A1 US20130288044A1 (en) 2013-10-31
US10787591B2 true US10787591B2 (en) 2020-09-29

Family

ID=49477561

Family Applications (1)

Application Number Title Priority Date Filing Date
US13/833,686 Active 2035-12-18 US10787591B2 (en) 2012-04-30 2013-03-15 Composites including silicon-oxy-carbide layers and methods of making the same

Country Status (5)

Country Link
US (1) US10787591B2 (enExample)
EP (2) EP3428311B1 (enExample)
JP (2) JP6421114B2 (enExample)
AU (1) AU2013287214B2 (enExample)
WO (1) WO2014007894A2 (enExample)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10991573B2 (en) 2017-12-04 2021-04-27 Asm Ip Holding B.V. Uniform deposition of SiOC on dielectric and metal surfaces
US11107673B2 (en) 2015-11-12 2021-08-31 Asm Ip Holding B.V. Formation of SiOCN thin films
US11158500B2 (en) 2017-05-05 2021-10-26 Asm Ip Holding B.V. Plasma enhanced deposition processes for controlled formation of oxygen containing thin films
US11195845B2 (en) 2017-04-13 2021-12-07 Asm Ip Holding B.V. Substrate processing method and device manufactured by the same
US11562900B2 (en) 2016-05-06 2023-01-24 Asm Ip Holding B.V. Formation of SiOC thin films
US12142479B2 (en) 2020-01-17 2024-11-12 Asm Ip Holding B.V. Formation of SiOCN thin films
US12341005B2 (en) 2020-01-17 2025-06-24 Asm Ip Holding B.V. Formation of SiCN thin films

Citations (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3745149A (en) 1971-09-29 1973-07-10 Nasa Preparation of polyimides from mixtures of monomeric diamines and esters of polycarboxylic acids
US5081198A (en) 1988-09-28 1992-01-14 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Tough, high performance, addition-type thermoplastic polymers
US5171822A (en) 1991-02-11 1992-12-15 The United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration Low toxicity high temperature pmr polyimide
US5338827A (en) 1990-01-30 1994-08-16 Trw Inc. Polyimide resins useful at high temperatures
US5412066A (en) 1994-03-03 1995-05-02 Ther United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Phenylethynyl terminated imide oligomers
US5654396A (en) 1983-09-27 1997-08-05 The Boeing Company Polyimide oligomers
WO1997038850A1 (en) 1996-04-15 1997-10-23 Monsanto Company Highly durable and abrasion-resistant dielectric coatings for lenses
US5826366A (en) * 1997-01-16 1998-10-27 Matibe; Jeffrey T. Illuminated fishing rod
US5853877A (en) * 1996-05-31 1998-12-29 Hyperion Catalysis International, Inc. Method for disentangling hollow carbon microfibers, electrically conductive transparent carbon microfibers aggregation film amd coating for forming such film
US5939521A (en) * 1998-01-23 1999-08-17 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Polyimides based on 4,4'-bis (4-aminophenoxy)-2,2'or 2,2', 6,6'-substituted biphenyl
US6124035A (en) 1999-04-13 2000-09-26 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration High temperature transfer molding resins
US6194036B1 (en) 1997-10-20 2001-02-27 The Regents Of The University Of California Deposition of coatings using an atmospheric pressure plasma jet
US6214451B1 (en) * 1996-12-10 2001-04-10 Takiron Co., Ltd. Formable antistatic resin molded article
US20040046497A1 (en) 2002-09-11 2004-03-11 General Electric Company Diffusion barrier coatings having graded compositions and devices incorporating the same
US20040180210A1 (en) * 2001-06-29 2004-09-16 Vissing Klaus D Article having a plasmapolymer coating and method for producing the same
US20050137383A1 (en) * 2001-05-17 2005-06-23 U. S. A. As Represented By The Administrator Of The National Aeronautics And Space Administration Space environmentally durable polyimides and copolyimides
US6949830B2 (en) 2002-10-30 2005-09-27 Fujitsu Limited Silicon oxycarbide, growth method of silicon oxycarbide layer, semiconductor device and manufacture method for semiconductor device
US6958192B2 (en) 2002-04-05 2005-10-25 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Polyimides from 2,3,3′,4′-biphenyltetracarboxylic dianhydride and aromatic diamines
US20060001040A1 (en) 2004-06-30 2006-01-05 General Electric Company High integrity protective coatings
US7041778B1 (en) 2003-06-05 2006-05-09 The United States Of America As Represented By The Secretary Of The Air Force Processable thermally stable addition polyimide for composite applications
JP2006123306A (ja) * 2004-10-28 2006-05-18 Dainippon Printing Co Ltd ガスバリア性積層体
WO2007044181A2 (en) 2005-10-05 2007-04-19 Dow Corning Corporation Coated substrates and methods for their preparation
US20070196633A1 (en) 2005-11-30 2007-08-23 Coak Craig E Durable transparent coatings for polymeric substrates
US20080051548A1 (en) * 2005-02-16 2008-02-28 Debbie Bailey Reinforced Silicone Resin Film and Method of Preparing Same
US20080206575A1 (en) 2006-11-30 2008-08-28 Warren Rosal Ronk Thermal oxidative barrier coatings for organic matrix composite substrates and coated articles
US20080213604A1 (en) 2006-05-12 2008-09-04 Stephen Mark Whiteker Organic Matrix Composite Structures and Thermal Oxidative Barrier Coating Therefor
US20080213486A1 (en) 2006-11-30 2008-09-04 Warren Rosal Ronk Methods for forming thermal oxidative barrier coatings on organic matrix composite substrates
US20080241506A1 (en) * 2004-09-23 2008-10-02 3M Innovative Properties Company Protected polymeric film
WO2008137588A1 (en) 2007-05-01 2008-11-13 Exatec, Llc Edge healing and field repair of plasma coating
US20080284971A1 (en) * 2007-05-18 2008-11-20 Samsung Electronics Co., Ltd. Flexible substrate for display device and display device using the same
US20080318067A1 (en) * 2004-05-14 2008-12-25 Dow Corning Toray Company, Ltd. Free Films Made Of Cured Organopolysiloxane Resins, Process For Production Thereof, And Laminated Films
US20090202817A1 (en) * 2006-06-16 2009-08-13 Saint-Gobain Glass France Method for depositing a hydrophobic/olelpyhobic lining using atmospheric plasma with improved durability
US20090221778A1 (en) * 2008-02-29 2009-09-03 Fujifilm Coporation Film
CA2380971C (en) * 1999-07-15 2009-12-29 Trespaphan Gmbh Paper-type plastic film
US20100092781A1 (en) * 2007-03-28 2010-04-15 Dow Corning Corporation Roll-To-Roll Plasma Enhanced Chemical Vapor Deposition Method of Barrier Layers Comprising Silicon And Carbon
JP2010158832A (ja) * 2009-01-08 2010-07-22 Mitsubishi Plastics Inc ガスバリア性フィルム
US20100279027A1 (en) 2009-05-04 2010-11-04 Pingree Liam S C System And Method For Applying Abrasion-Resistant Coatings
US20120035057A1 (en) * 2010-08-03 2012-02-09 Alexandre Bratkovski Room-temperature superconductive-like diode device

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3232124B2 (ja) * 1992-05-20 2001-11-26 鐘淵化学工業株式会社 硬化性組成物
JP4066229B2 (ja) * 2001-02-14 2008-03-26 株式会社カネカ 硬化剤、硬化性組成物、光学材料用組成物、光学材料、その製造方法、並びに、それを用いた液晶表示装置及びｌｅｄ
CN101848914B (zh) * 2007-11-09 2013-09-11 Kaneka株式会社 环状聚有机硅氧烷的制备方法、固化剂、固化性组合物及其固化物
JP2011039283A (ja) * 2009-08-11 2011-02-24 Konica Minolta Holdings Inc 調光素子

Patent Citations (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3745149A (en) 1971-09-29 1973-07-10 Nasa Preparation of polyimides from mixtures of monomeric diamines and esters of polycarboxylic acids
US5654396A (en) 1983-09-27 1997-08-05 The Boeing Company Polyimide oligomers
US5081198A (en) 1988-09-28 1992-01-14 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Tough, high performance, addition-type thermoplastic polymers
US5338827A (en) 1990-01-30 1994-08-16 Trw Inc. Polyimide resins useful at high temperatures
US5171822A (en) 1991-02-11 1992-12-15 The United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration Low toxicity high temperature pmr polyimide
US5412066A (en) 1994-03-03 1995-05-02 Ther United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Phenylethynyl terminated imide oligomers
WO1997038850A1 (en) 1996-04-15 1997-10-23 Monsanto Company Highly durable and abrasion-resistant dielectric coatings for lenses
US5853877A (en) * 1996-05-31 1998-12-29 Hyperion Catalysis International, Inc. Method for disentangling hollow carbon microfibers, electrically conductive transparent carbon microfibers aggregation film amd coating for forming such film
US6214451B1 (en) * 1996-12-10 2001-04-10 Takiron Co., Ltd. Formable antistatic resin molded article
US5826366A (en) * 1997-01-16 1998-10-27 Matibe; Jeffrey T. Illuminated fishing rod
US6194036B1 (en) 1997-10-20 2001-02-27 The Regents Of The University Of California Deposition of coatings using an atmospheric pressure plasma jet
US5939521A (en) * 1998-01-23 1999-08-17 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Polyimides based on 4,4'-bis (4-aminophenoxy)-2,2'or 2,2', 6,6'-substituted biphenyl
US6124035A (en) 1999-04-13 2000-09-26 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration High temperature transfer molding resins
CA2380971C (en) * 1999-07-15 2009-12-29 Trespaphan Gmbh Paper-type plastic film
US20050137383A1 (en) * 2001-05-17 2005-06-23 U. S. A. As Represented By The Administrator Of The National Aeronautics And Space Administration Space environmentally durable polyimides and copolyimides
US20040180210A1 (en) * 2001-06-29 2004-09-16 Vissing Klaus D Article having a plasmapolymer coating and method for producing the same
US6958192B2 (en) 2002-04-05 2005-10-25 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Polyimides from 2,3,3′,4′-biphenyltetracarboxylic dianhydride and aromatic diamines
US20040046497A1 (en) 2002-09-11 2004-03-11 General Electric Company Diffusion barrier coatings having graded compositions and devices incorporating the same
WO2004025749A2 (en) 2002-09-11 2004-03-25 General Electric Company Diffusion barrier coatings having graded compositions and devices incorporating the same
JP2005537963A (ja) 2002-09-11 2005-12-15 ゼネラル・エレクトリック・カンパニイ 傾斜組成を有する拡散障壁コーティング及びそれを含むデバイス
US6949830B2 (en) 2002-10-30 2005-09-27 Fujitsu Limited Silicon oxycarbide, growth method of silicon oxycarbide layer, semiconductor device and manufacture method for semiconductor device
US7041778B1 (en) 2003-06-05 2006-05-09 The United States Of America As Represented By The Secretary Of The Air Force Processable thermally stable addition polyimide for composite applications
US20080318067A1 (en) * 2004-05-14 2008-12-25 Dow Corning Toray Company, Ltd. Free Films Made Of Cured Organopolysiloxane Resins, Process For Production Thereof, And Laminated Films
US20060001040A1 (en) 2004-06-30 2006-01-05 General Electric Company High integrity protective coatings
US20080241506A1 (en) * 2004-09-23 2008-10-02 3M Innovative Properties Company Protected polymeric film
JP2006123306A (ja) * 2004-10-28 2006-05-18 Dainippon Printing Co Ltd ガスバリア性積層体
WO2007089218A2 (en) 2004-11-15 2007-08-09 General Electric Company High integrity protective coating
JP2008520477A (ja) 2004-11-15 2008-06-19 ゼネラル・エレクトリック・カンパニイ 高保全性保護被膜
US20080051548A1 (en) * 2005-02-16 2008-02-28 Debbie Bailey Reinforced Silicone Resin Film and Method of Preparing Same
WO2007044181A2 (en) 2005-10-05 2007-04-19 Dow Corning Corporation Coated substrates and methods for their preparation
JP2009511290A (ja) 2005-10-05 2009-03-19 ダウ・コーニング・コーポレイション 被覆基板及びその製造方法
US20070196633A1 (en) 2005-11-30 2007-08-23 Coak Craig E Durable transparent coatings for polymeric substrates
US20080213604A1 (en) 2006-05-12 2008-09-04 Stephen Mark Whiteker Organic Matrix Composite Structures and Thermal Oxidative Barrier Coating Therefor
US7776434B2 (en) 2006-05-12 2010-08-17 General Electric Company Organic matrix composite structures and thermal oxidative barrier coating therefor
US20090202817A1 (en) * 2006-06-16 2009-08-13 Saint-Gobain Glass France Method for depositing a hydrophobic/olelpyhobic lining using atmospheric plasma with improved durability
JP2009539754A (ja) 2006-06-16 2009-11-19 サン−ゴバン グラス フランス 大気圧プラズマを用いて耐久性が改善された疎水性／疎油性ライニングを堆積させる方法
US20080213486A1 (en) 2006-11-30 2008-09-04 Warren Rosal Ronk Methods for forming thermal oxidative barrier coatings on organic matrix composite substrates
US7776433B2 (en) 2006-11-30 2010-08-17 General Electric Company Thermal oxidative barrier coatings for organic matrix composite substrates and coated articles
US7776404B2 (en) 2006-11-30 2010-08-17 General Electric Company Methods for forming thermal oxidative barrier coatings on organic matrix composite substrates
US20080206575A1 (en) 2006-11-30 2008-08-28 Warren Rosal Ronk Thermal oxidative barrier coatings for organic matrix composite substrates and coated articles
US20100092781A1 (en) * 2007-03-28 2010-04-15 Dow Corning Corporation Roll-To-Roll Plasma Enhanced Chemical Vapor Deposition Method of Barrier Layers Comprising Silicon And Carbon
WO2008137588A1 (en) 2007-05-01 2008-11-13 Exatec, Llc Edge healing and field repair of plasma coating
US20080284971A1 (en) * 2007-05-18 2008-11-20 Samsung Electronics Co., Ltd. Flexible substrate for display device and display device using the same
US20090221778A1 (en) * 2008-02-29 2009-09-03 Fujifilm Coporation Film
JP2010158832A (ja) * 2009-01-08 2010-07-22 Mitsubishi Plastics Inc ガスバリア性フィルム
US20100279027A1 (en) 2009-05-04 2010-11-04 Pingree Liam S C System And Method For Applying Abrasion-Resistant Coatings
WO2010129149A1 (en) 2009-05-04 2010-11-11 The Boeing Company Coating method
US20120035057A1 (en) * 2010-08-03 2012-02-09 Alexandre Bratkovski Room-temperature superconductive-like diode device

Non-Patent Citations (21)

* Cited by examiner, † Cited by third party
Title
CAS Registry No. 39345-87-4 SciFinder (ACS) 2016. *
CAS RN 78392-33-3PMR-15 polyimide SciFinder (2017). *
Derwent Acc-No. 1993-309256 (1993). *
English machine translation from JPO for JP 2010158832 (2010). *
English machine translation of 2006123306 JPO (2006). *
International Search Report and Written Opinion for Application No. PCT/US2013/034435 dated Jan. 21, 2014.
JAN SCH�FER, STEFAN HORN, R�DIGER FOEST, RONNY BRANDENBURG, PETR VAŠINA, KLAUS-DIETER WELTMANN: "Complex analysis of SiOxCyHz films deposited by an atmospheric pressure dielectric barrier discharge", SURFACE AND COATINGS TECHNOLOGY, ELSEVIER BV, AMSTERDAM, NL, vol. 205, 1 July 2011 (2011-07-01), AMSTERDAM, NL, pages S330 - S334, XP055419593, ISSN: 0257-8972, DOI: 10.1016/j.surfcoat.2011.03.124
Office Action for European Patent Application No. 13 783 121.0 dated Mar. 31, 2017.
Office Action for Japanese Application No. 2015-510287 dated May 8, 2018.
Office Action for Japanese Application No. 2018-159930 dated Jun. 18, 2019, 5 pages.
Office Action for Japanese Patent Application No. 2015-510287 dated Apr. 4, 2017.
Office Action for Japanese Patent Application No. 2015-510287 dated Oct. 31, 2017, 8 pages.
Oxidation Protective Barrier Coatings for Hi-T PMC, David Harding, J. Mater. Res., vol. 9, No. 6, Jun. 1994. *
Reinforcement, Polymer Encyclopedia. *
Schafer, Jan et al.; "Complex analysis of SiOxCyHz films deposited by an atmospheric pressure dielectric barrier discharge"; Surface and Coatings Technology; vol. 205, Jul. 1, 2011; pp. S330-S334; XP055419593.
SERGEI STAROSTINE, EUGEN ALDEA, HINDRIK DE VRIES, MARIADRIANA CREATORE, M. C. M. VAN DE SANDEN: "Atmospheric Pressure Barrier Discharge Deposition of Silica-Like Films on Polymeric Substrates", PLASMA PROCESSES AND POLYMERS, WILEY-VCH VERLAG GMBH & CO. KGAA, vol. 4, no. S1, 1 April 2007 (2007-04-01), pages S440 - S444, XP055130721, ISSN: 16128850, DOI: 10.1002/ppap.200731203
Starostin S. et al.; "High current diffuse dielectric barrier discharge in atmospheric pressure air for the deposition of thin silica-like films"; Applied Physics Letters; vol. 96, No. 6; Feb. 9, 2010; pp. 61502-61502; XP012132113.
STAROSTIN S.; PREMKUMAR P.; CREATORE M.; DE VRIES H.; PAFFEN R.; VAN DE SANDEN M.: "High current diffuse dielectric barrier discharge in atmospheric pressure air for the deposition of thin silica-like films", APPLIED PHYSICS LETTERS, A I P PUBLISHING LLC, US, vol. 96, no. 6, 9 February 2010 (2010-02-09), US, pages 061502 - 061502-3, XP012132113, ISSN: 0003-6951, DOI: 10.1063/1.3310024
Starostine S. et al.; "Atmospheric pressure barrier discharge deposition of silica-like films on polymeric substrates"; Plasma Processes and Polymers; vol. 4, No. S1; Apr. 1, 2007; pp. S440-S444; XP055130721.
Summons to Attend Oral Proceedings from corresponding European Patent Application No. 13 783 121.0 dated Nov. 22, 2017, 6 pages.
Tsotsis, T.K.; "Thermo-Oxidative Ageing in Composites"; Ageing of Composites; Woodhead Publishing, Ltd., Cambridge, UK, Jan. 2008, p. 130-159.

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11107673B2 (en) 2015-11-12 2021-08-31 Asm Ip Holding B.V. Formation of SiOCN thin films
US11996284B2 (en) 2015-11-12 2024-05-28 Asm Ip Holding B.V. Formation of SiOCN thin films
US11562900B2 (en) 2016-05-06 2023-01-24 Asm Ip Holding B.V. Formation of SiOC thin films
US12272546B2 (en) 2016-05-06 2025-04-08 Asm Ip Holding B.V. Formation of SiOC thin films
US11195845B2 (en) 2017-04-13 2021-12-07 Asm Ip Holding B.V. Substrate processing method and device manufactured by the same
US11158500B2 (en) 2017-05-05 2021-10-26 Asm Ip Holding B.V. Plasma enhanced deposition processes for controlled formation of oxygen containing thin films
US11776807B2 (en) 2017-05-05 2023-10-03 ASM IP Holding, B.V. Plasma enhanced deposition processes for controlled formation of oxygen containing thin films
US10991573B2 (en) 2017-12-04 2021-04-27 Asm Ip Holding B.V. Uniform deposition of SiOC on dielectric and metal surfaces
US12142479B2 (en) 2020-01-17 2024-11-12 Asm Ip Holding B.V. Formation of SiOCN thin films
US12341005B2 (en) 2020-01-17 2025-06-24 Asm Ip Holding B.V. Formation of SiCN thin films

Also Published As

Publication number Publication date
WO2014007894A2 (en) 2014-01-09
EP3428311A1 (en) 2019-01-16
JP2019022984A (ja) 2019-02-14
EP3428311B1 (en) 2022-05-04
WO2014007894A3 (en) 2014-03-20
US20130288044A1 (en) 2013-10-31
JP2015523917A (ja) 2015-08-20
JP6421114B2 (ja) 2018-11-07
AU2013287214A1 (en) 2014-08-28
EP2844783A2 (en) 2015-03-11
EP2844783B1 (en) 2018-08-15
AU2013287214B2 (en) 2016-04-14

Similar Documents

Publication Publication Date Title
US10787591B2 (en) Composites including silicon-oxy-carbide layers and methods of making the same
US20080102206A1 (en) Multilayered coatings for use on electronic devices or other articles
US7737525B1 (en) Method for producing low-K CDO films
JP2007237588A (ja) ガスバリア性フィルム及びその製造方法
EP1927619B1 (en) Methods for forming thermal oxidative barrier coatings on organic matrix composite substrates
CN103187455A (zh) 用于电子器件或其它制品上的涂层的杂化层
Cech et al. Surface modification of glass fibers by oxidized plasma coatings to improve interfacial shear strength in GF/polyester composites
EP1927614B1 (en) Thermal oxidative barrier coatings for organic matrix composite substrates and coated articles
WO2009080610A1 (en) A substrate coated with amorphous hydrogenated carbon
Gao et al. Deposition of thin films on glass fiber fabrics by atmospheric pressure plasma jet
KR20170095279A (ko) 향상된 기체 투과성을 갖는 내마모성 광학 제품
Jousseaume et al. Porous ultra low k deposited by PECVD: From deposition to material properties
Ding et al. Open-air spray plasma deposited UV-absorbing nanocomposite coatings
Cech et al. Plasma-polymerized versus polycondensed thin films of vinyltriethoxysilane
Cui et al. Carbon-bridge incorporation in organosilicate coatings using oxidative atmospheric plasma deposition
Xiong et al. Deposition of thin films on basalt fibers surface by atmospheric pressure plasma with different siloxane precursors
Cech et al. Chemistry of Plasma‐Polymerized Vinyltriethoxysilane Controlled by Deposition Conditions
Ramamoorthy et al. The influence of process parameters on chemistry, roughness and morphology of siloxane films deposited by an atmospheric plasma jet system
Khodabakhshi Palandi et al. Surface Texturing of Medium-Density Fiberboard (MDF) Using Atmospheric Plasma for Enhanced Hydrophobicity
Moriche et al. Tunable structure and connectivity of organosilica hybrid films by using different epoxy based precursors in atmospheric plasma deposition
Rahman et al. Effect of process parameters on chemistry, growth rate and nano-sized particulate formation of atmospheric plasma deposited, nm thick siloxane coatings
US20050221003A1 (en) Enhancement of SiO2 deposition using phosphorus (V) compounds
Jousseaume et al. PECVD versus spin-on to perform porous ULK for advanced interconnects: chemical composition, porosity and mechanical behavior
Cech et al. Analysis of annealed thin polymer films prepared from dichloro (methyl) phenylsilane by plasma polymerization
Yu et al. Silicon dioxide thin film derived from polyphenylcarbosilane under an oxidizing atmosphere

Legal Events

Date Code Title Description
AS Assignment

Owner name: THE BOEING COMPANY, ILLINOIS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TSOTSIS, THOMAS K.;MATOS, MARVI A.;RANADE, ALPANA;AND OTHERS;SIGNING DATES FROM 20130311 TO 20130313;REEL/FRAME:030011/0461

STCV Information on status: appeal procedure

Free format text: EXAMINER'S ANSWER TO APPEAL BRIEF MAILED

STCV Information on status: appeal procedure

Free format text: APPEAL AWAITING BPAI DOCKETING

STCV Information on status: appeal procedure

Free format text: ON APPEAL -- AWAITING DECISION BY THE BOARD OF APPEALS

STCV Information on status: appeal procedure

Free format text: BOARD OF APPEALS DECISION RENDERED

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4